The present invention relates to catalysts for atom transfer radical polymerization processes. Specifically, the present invention relates to a hybrid catalyst system comprising transition metal complexes held in close conjunction with a solid support and of a soluble ligand, or soluble transition metal complex or desorbed catalyst.
There is a continuing effort in polymer chemistry to develop new polymerization processes and new polymers. A relatively recent development in polymer chemistry has been the development of controlled or living polymerization processes. A controlled or living polymerization process is one in which chain transfer and termination reaction are essentially nonexistent relative to the polymer propagation reaction. These developments have led to the production of polymers that exhibit macro functionality and to the development of functional polymers that possess specific chemical reactivity. The new polymers extend the level of control available to materials e engineers in processing polymers and using polymers as building blocks in, or components for, subsequent material forming reactions, such as copolymerizations, chain extensions and crosslinking reactions, and interaction with substrates, including dispersed solids.
A significant economic hurdle which continually needs to be overcome in this effort is to provide the benefits of controlled polymerization from available low cost monomers in available commercial process equipment. These long term objectives have provided the backdrop, or driving force, for the continuing advances in controlled polymerization of radically (co)polymerizable monomers, disclosed in earlier patent applications, and provide the incentive to extend, simplify and make more robust the process known as atom transfer radical polymerization (ATRP).
The recently developed ATRP process and polymers developed from the classic ATRP reaction are described in U.S. patent application Ser. No. 09/018,554 and 09/534,827, the entire contents of which are hereby incorporated herein by reference. Methods for exercising control over many parameters in a catalytic process for the controlled polymerization of a wide range of free radically (co)polymerizable monomers have been described in publications authored or co-authored by Krzysztof Matyjaszewski and others. See for example, Wang, J. S. and Matyjaszewsk, K., J. Am. Chem. Soc., vol. 117, p. 5614 (1995); Wang, J. S. and Matyjaszewsk, K., Macromolecules, vol. 28, p. 7901 (1995); K. Matyjaszewski et al., Science, vol. 272, p.866 (1996); K. Matyjaszewski et al., xe2x80x9cZerovalent Metals in Controlled/xe2x80x9clivingxe2x80x9d Radical Polymerization,xe2x80x9d Macromolecules, vol. 30, pp. 7348-7350 (1997); J. Xia and K. Matyjaszewski, xe2x80x9cControlled/xe2x80x9cLivingxe2x80x9d Radical Polymerization. Homogenous Reverse Atom Transfer Radical Polymerization Using AIBN as the Initiator,xe2x80x9d Macromolecules, vol. 30, pp. 7692-7696 (1997); U.S. patent application Ser. No. 09/126,768, the entire contents of which are hereby incorporated by reference; U.S. Pat. Nos. 5,807,937, 5,789,487, 5,910,549, 5,763,548, 5,789,489, 5,945,491, 6,111,022, 6,121,371, 6,124,411 and U.S. patent application Ser. Nos. 09/034,187, 09/018,554, 09/431,871, 09/359,359, 09/359,591, 09/369,157, and 09/534,827 the entire contents of each are hereby incorporated herein by reference. The subtle interactions between the parameters have been further explored and implementation of the teachings disclosed in these publications has allowed the preparation of many inherently useful novel materials displaying control over functionality and topology, and production of novel tele-functional building blocks for further material forming reactions, resulting from application of the site specific functional and topological control attainable through this robust controlled polymerization process for free radically (co)polymerizable monomers.
The system or process employed to gain control over the polymerization of free radically (co)polymerizable monomers has been described in earlier applications as comprising the use of four components: (i) an initiator molecule; (ii) a transition metal compound having (iii) an added or associated counterion and the transition metal compound complexed with (iv) a ligand(s). The initiator molecule, or polymerization originator molecule may be any molecule comprising one or more radically transferable atom(s) or group(s) capable of participating in a reversible redox reaction with the transition metal compound. The transition metal compound may include an added or associated counterion and comprise a transition metal salt. So that all reactive oxidation states are soluble to some extent in the reaction medium, the transition metal may be complexed with the ligand(s). The components of the system may be optimized to provide more precise control for the (co)polymerization of the free radically polymerizable monomers. See U.S. Pat. No. 5,763,548, the entire contents of which are hereby incorporated herein by reference.
In an embodiment known as xe2x80x9creversexe2x80x9d ATRP, the initiator molecule described above can be formed in-situ by reaction of a free radical with the redox conjugate of the transition metal compound. Other components of the polymerization system such as the choice of the radically transferable atom or group, counterion initially present on the transition metal, and optional solvent may influence the process. U.S. Pat. No. 5,807,937 provides as an example of a single molecule containing a combination of functions, a complex in which the counterion and ligand components are in one molecule. The role of a deactivator, the xe2x80x9cpersistent radical,xe2x80x9d or for ATRP, the transition metal redox conjugate, is also described in U.S. Pat. No. 5,807,937.
While not to be limited to the following description, the theory behind ATRP disclosed in the previous work is that polymerization proceeds essentially by cleavage (and preferably essentially homolytic cleavage) of the radically transferable atom or group from the initiator molecule or, during the polymerization process the dormant polymer chain end, by a reversible redox reaction with a complexed transition metal catalyst, without any strong carbon-transition (Cxe2x80x94Mt) bond formation between the active growing polymer chain end and the transition metal complex. Within this theory as the transition metal complex, in a lower active oxidation state, or in its activator state, activates the initiator or dormant polymer chain end by homolytically removing the radically transferable atom or group from the initiating molecule, or growing polymer chain end, in a reversible redox reaction, an active species is formed that allows other chemistry, essentially free radical based chemistry to be conducted. The transition metal complex in the higher oxidation state, the redox conjugate state or deactivator state, transfers a radically transferable atom or group to the active initiator molecule or growing chain end, thereby reforming the lower oxidation state transition metal complex. When free radical based chemistry occurs, a new molecule comprising a radically transferable atom or group is also formed. In prior publications, the catalytically active transition metal compound, which can be formed in situ or added as a preformed complex, has been described as containing a range of counterions. The counterion(s) may be the same as the radically transferable atom or group present on the initiator, for example a halide such as chlorine or bromine, or may be different radically transferable atoms or groups. An example of the latter counterion is a chloride counterion on the transition metal compound when the initiator first contains a bromine. Such a combination allows for efficient initiation of the polymerization followed by a controlled rate of polymerization, and has additionally been shown to be useful in certain crossover reactions, from one set of (co)monomers to a second set of (co)monomers, allowing efficient formation of block copolymers.
ATRP is one of the most promising methods in the field of controlled/xe2x80x9clivingxe2x80x9d radical polymerizations, one which can be applied to a wide variety of monomers and provide well defined polymers. However, one of the commercial limitations of ATRP is the presence of a transition metal complex, which is often present win concentrations above what is normally considered catalytic levels that can be left in the products. Therefore is some applications, the catalyst should be removed after the polymerization. Several processes for the preparation and use of immobilized ATRP catalysts have been proposed to reduce the concentration of catalyst remaining in the polymer product. Processes have been attempted using ATRP catalysts immobilized on silica, crosslinked polystyrene beads or attached to polymer chain; all of which can provide an efficient way conducting the polymerization or be used for separating and recycling of the catalyst. However, generally these techniques still suffer, to some degree, from a lack of the control over the polymerization originating from the heterogeneous nature of the process. Not wishing to be limited by the description of the mechanism, this loss of control may be attributable to an insufficient deactivation rate of the growing radical which results from the slow diffusion of the active growing polymer chains to the immobilized deactivator complexes, which leads to a much higher molecular weight and broader molecular weight distribution than in homogeneous systems.
Thus, there exists a need for an catalyst system for controlled polymerization that is easily separable from the reaction medium and provides sufficient control over the process. More, specifically there exists a need for a catalyst system for ATRP which allows sufficient deactivation of the growing polymer chains to provide a controlled polymerization process.
The present invention meets these needs by providing a polymerization process comprising polymerizing radically (co)polymerizable monomers in the presence of a system comprising an initiator comprising one or more radically transferable atom(s) or group(s) and a catalyst system comprising a transition metal, one or more counterions, a ligand attached to a solid support, and a soluble ligand. The present invention also provides polymerization process comprising polymerizing radically (co)polymerizable monomers in the presence of a system comprising an initiator comprising one or more radically transferable atom(s) or group(s), an attached transition metal complex, and a soluble transition metal complex.
The ligand or the transition metal complex may be physico- or physicochemically or chemically bound to the surface of a solid support through ionic bonding, physisorption, chemisorption, Van der Waals forces, coordinate or covalent bonding. The soluble transition metal complex or ligand may be formed by changing a (co)polymerization condition to cause at least a portion of the transition metal complex or ligand to be unbound from the surface of the added solid. A process for the removal and recycle of a supported transition metal catalyst complex from a polymerization reaction medium comprising separating the supported transition metal catalyst from the reaction medium, and contacting the supported transition metal catalyst with a reducing agent is also provided.